Process of making formaldehyde sulfoxylates.



RUDOLF Mf'lLL-ER AND .-WOLDEMAR WOLLENBERG, or Hooiisr oN-THE- MAIN, GERMANY, AssicNoRs TO FARBWERKE, V-ORM. MEisrEa' LUCIUS & BRUNIN'G, OF HOGHST-ONJIHE-MAIN,'GERMANY, A CORPO- RATION OF GERMANY.

- PROCESS OF-MAKING: YFORMALDIEHYDE SULFOXYLATES.

Specification of Letters Patent. I

Patented. J an. 22, 1907.

Application filed March 20,1906. vi Serial N el 307.032. (Specimens) To all mil/m it may concern.-

Be it known that we, RUDoLF Mt'in En,

Ph. D., and WOLDEMAR W LLENBER Phl- D chemists, citizens of the Empire of Germany, residing at H6chst-onthe-Main, Ger many,,have invented certain new and useful Improvements in Formaldehyde Sulfoxylates and Processes of Making Same, of which the following is a specification. v

As by the action of formaldehyde on h drosulfite 'ketone sulfoxylates mayv also ev obtained by the action ofacetqne or ethylmeth lketone on alkaline hydrosulfites, which may e isolated afterward. by crystallization is These ketone s'ulfoxylates can also be produced by reducing the products of reaction of bisulfites, sulfurous acid, or hydro sulfite on acetone or ethylmethylketone or by subject'- ing these compounds to reduction in press ence of said ketones;

The ketone sulfoxylates are obtained, for instance, as follows: Into asolution of sixtyfive parts of acetone in one thousand parts of water are introduced sixty-four parts of sul- 2 5 fur dioxid. One hundred and twenty parts of zinc-dust are thcn'addedwhile stirring and well cooling, and if no further spontaneous heating occurs thetemperature is raised to 50 to 60 ccntigrade. After heating for some hours a solution of acetone .zinc sulfoxylate is obtained, which when treated with sodium carbonate is transformed int acetone sodium sulfoxylate. v

We have found that lretone sulfoxylates may be transformed into the more stable formaldehyde sulfoxylates if the former are treated with formaldehyde. By the action of the formaldehyde on kctonc sulfoxylatcs' theketone is eliminated with formation of 4 formaldehyde sulfoxylate, which is readily observed in that thesolution of the ketone sulfoxylates treated with the equivalent proportion offormaldehyde no longer reduces indigo-sulfonic acid in the cold. The reaction of this process may be interpreted by the following equation:

The rocess for obtaining formaldehyde sulfoxy ate from ketone sulfoxylates may be carried out, for instance, as follows: To a solution containing one hundred and forty parts of acetone sodium sulfoxylate of one hundred percent. strength in one liter of water are added while stirring seventy five parts of formaldehyde of fortyper -cent. strength. -The combination occurs rapidly, and the formaldehyde sodium sulfoxylate may then be obtained in solid form by evaporating in a vacuum, While the acetone is dis tilled ofi. For the acetone sodium sulfoxylate other salts-such, for instance, as the zinc salt-may be used in a like manner.

Having now described our invention, what' we claim'is 1. The herein-described process for the manufacture of formaldehyde sulfoxylates, which consists in treating the sulfoxylates of ketones having the. formula CH COX, wherein X means methyl or ethyl, with formaldeiyde. 2. The herein-described process for the "manufacture of formaldehyde sulfoxylates, which consists in treating the sulfoxylates of acetone with formaldehyde.

In testimony that we claim the foregoing as our invention we have signed our names in preseni ze of two subscribing witnesses.

\ UDOLF MULLER.

VVOLDEMAR VVOLLENBERG. Witnesses:

JEAN GRUND,

CAPL GR ND. 

